Copper-containing azo dyestuffs



Patented Dec. 2, 1952 UNITED STATES PATENT OFFICE COPPER-CONTAINING AZO DYESTUFFS Walter Wehrli, Basel, Switzerland, assignor to Sandoz Limited, Basel, Switzerland; a Swiss firm No Drawing. Application January 16, 1951, Se-

rial No. 206,312. In Switzerland August 24,

6 Claims. (01. 260-148) 1 2 The present application is a continuation-inall the dilficulties encountered with the compart of my copending application Ser. No. 604,727 pounds according to Stiisser et al. are eliminated, filed on July 12, 1945 (now abandoned). and the full coppering of the disazo dyestuffs may The present invention relates to the manube realized without superatmospheric pressures or iacture of new copper compounds of polyazo 5 temperatures above 100 C. The coppering dyestuffs and to the new compounds themselves. proceeds smoothly and yields fully coppered dye- It is well known that copper-containing disazo stuffs possessing excellent fastness to light and dyestuffs corresponding to the formula to Wet treatments.

( 13 on on on HO3S- -SO3H HOsS- NHR T0112 wherein R stands for a hydrogen atom or for a In preparing the new copper complexes achydrocarbon or an acyl radical, may be prepared cording to the present invention, a starting comby the process described by Stiisser et al. in U. S. pound corresponding to the formula S0311 OH 0on3 00H: on

I I l H0 8 SO3H H035 NHR Patent No. 1,889,732. In order to produce the wherein It stands for a mononuclear aryl radical copper complexes it is necessary to heat the of the benzene series, an acetyl group or a benstarting materials for along time in an autoclave zoyl group, is subjected to a gentle boiling in to temperatures of about 110ll5 C., the usual an aqueous solution in presence of cupramcoppering methods giving only partial coppering monium ions and an alkaline substance such as and therefore dyestuffs the fastness of which sodium carbonate or potassium carbonate. The to light and to wet treatments do not respond to mononuclear aryl radical may be a substituted the requirements of the dyeing industry. or unsubstituted henyl group, such as the phenyl It is a primary object of the present invention group itself, or the alkylphenyl (e. g. methylto obviate the defects of this state of the art and phenyl) or alkoxyphenyl (e. g. methoxyphenyl) to embody a process whereby the coppering may groups, etc. The coppering proceeds rapidly with be carried out without the necessity of working splitting oi? oi the methyl groups attached to in an autoclave and at temperatures higher than the oxygen atoms of the diphenyl derivative, and the boiling point of water. It is a further object uniform copper complexes, which then can be of the invention to produce fully coppered dyesalted out from the solution, are obtained. stufis of excellent fastness to light and to wet The new copper-containing disazo dyestuffs treatments. thus obtained correspond to the formula SOsH OH .1 These objects are realized according to the are easily soluble in water, possess excellent present invention with the aid of starting disazo afiinity for cellulose fibers and dye them in bright dyestuffs of the type of dyestuff (I) supra, but blue'shades of excellent fastness to light and wet which contain at least 3 sulfonic acid groups in treatments. the left-hand a-naphthol radical in the 3-, 6- The following examples illustrate the present and 8-positions. With these starting compounds, invention, the parts being by weight.

p 9,620,331 3 4 Example 1 Example 2 100 parts of the dyestufi of the formula The process according to Example 1 is repeated except that the starting dyestufi is replaced by an equivalent quantity of the dyestufi of the are dissolved in 2000 parts of water with addition of 20 parts of sodium carbonate. To this solution there are added, portionwise and while formula soarr OH 00133 00113 011 Ho3s- -so311 Ho3s -NH-Ocn whereby the resultant copper complex corresponds to the formula stirring at 80-90" C., 500 parts of an aqueous solution containing 50 parts of crystallized copper S0311 OH HOaS SOalI H038- sulphate and 85 parts of a concentrated aqueous Example 3 ammonia solution. The mixture is stirred for 5 hours at 80-90 C. and heated to boiling within 1 By replacing the starting dyestuff of Example 1 by an equivalent quantity of the dyestuff of the hour. The solution is then boiled for 15 hours formula sour on OCH: 0am on N=N- N=N- no3s SO:H HOsS- NHC O CH:

under reflux. The complex copper compound and otherwise proceeding in the manner de- SO H OH 011 OH on N=N N=N Hois- -so3H 1103sthus produced is salted out, filtered and dried. scribed in such example, the dyestufi of the for- It is soluble in water with a blue coloration and mula is obtained.

in concentrated sulphuric acid with a greenishblue coloration. It dyes cotton and regenerated cellulose in clear blue shades possessing very good fastness to light, to washing and to water.

Example 4 100 parts of the dyestuff of the formula Hots OH 00113 OCH; OH

HOzS- -s 0311 HOaS- NH--C 0-6 5 6 are dissolved in 2000 parts of water with addi- 4- by an equivalent quantity: of the dyestuff slof tion of 20 parts of sodium carbonate. To this the formula .1 3.

S0311 OH mm 00113 on" HOaS- SOaH HOaS- NH-OO-CH:A

solution are added, portionwise and while stirring at 80-90 0., 500 parts of an aqueous solution and otherwise proceeding in the manner de.-' scribed in, such-example, the. dyestufi oi the containing 50 parts of crystallized copper sulformula 5 30311 011 OH OH OH N=N N=N HOaS- SOaH HOsS- NH CO OHa phate and 85 parts of a concentrated aqueous 20 is obtained.

ammonia solution. The mixture is stirredv for 5 hours at 80-90 c. and heated to boiling with- 51; i dlscmsed the What 15 in 1 hour. The solution is then boiled for 15 hours under reflux. The complex copper com- 1. A copper complex compound of the formula Cuz pound A wherein R stands for a member selected from the sou-1 OH 011 on V "on; 1" d HOaS- -solH HOaS NHO 0-6 group consisting of phenyl, alkylphenyl, alkoxyphenyl, acetyl, and benzoyl radicals.

2. The copper complex compound of the formula thus produced is salted out, filtered and dried. It is soluble in water with a blue coloration and in concentrated sulphuric acid with a greenishblue coloration. It dyes cotton and regenerated SOaH OH cellulose in clear blue shades possessing very 3. The copper complex compound of the good fastness to light, to washing and to water. formula s our on OH 011 011 HOaS- SOaH HOaS- NH C -OHs --Gu l Example 5 4. The copper complex compound of the By replacing the starting dyestuff of Example formula SOzH OH OH OH OH N=N QM. HOaS- -SOaH Hots NH-O-OCHa 5. The copper complex compound of the formula formula SOaH OH 6. The copper complex compound of the SOSH OH OH OH OH OH OH WAL'IER WEHRLI.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS 

1. A COPPER COMPLEX COMPOUND OF THE FORMULA 